Secondary recovery of petroleum

ABSTRACT

This invention relates to the secondary recovery of petroleum, and in particular, involves a process for reducing the amount of water recovered from a producing well in a water flooding process for recovering petroleum from a subterranean oil-bearing formation. This reduction in water is accomplished by introducing a stable liquid dispersion of a water soluble anionic vinyl addition polymer and a water soluble cationic polymer.

United States Patent [191 Bott 51*Dec. 18, 1973 SECONDARY RECOVERY OFPETROLEUM [75] Inventor: Lawrence L. Bott, Oak Park, Ill.

[73] Assignee: Nalco Chemical Company, Chicago,

Ill.

[ Notice: The portion of the term of this patent subsequent to Mar. 19,1990, has been disclaimed.

[22] Filed: Dec. 2, 1971 [21] Appl. No.: 204,322

[52] US. Cl 166/276, 166/278, 166/305 R [51] Int. Cl E2lb 43/02 [58]Field of Search [66/275, 276, 278,

[56] References Cited UNITED STATES PATENTS 3,721,295 3/1973 Bott166/294 3,416,601 12/1968 Young et a1. 166/276 2,356,254 8/1944 Blair,Jr. et al. 166/305 R 3,540,532 11/1970 Davis, Jr. et al 166/275 PrimaryExaminer-Marvin A. Champion Assistant Examiner-Jack E. Ebel Atmrney.lohnG. Premo et al.

[57] ABSTRACT 5 Claims, No Drawings SECONDARY RECOVERY OF PETROLEUMINTRODLJCTION The technique of water flooding to recover crude oil fromsubterranean formations is well known and is described in U. S. Pat.Nos. 2,827,964 and 3,399,725. This process involves injecting an aqueousflooding medium into the oil-bearing formation through an input wellpenetrating the formation. This provides the energy and flushing actionnecessary to force oil remaining within the formation into nearby outputwells penetrating the same formation. The efficiency of such a recoveryprocess will vary with the heterogeneity of the formation, i.e.,variability in the permeability of the formation, and the viscosity ofthe oil to be displaced.

It has generally been considered uneconomical to employ water-floodingtechniques to recover high viscosity oils. The wide difference betweenthe viscosity of the residual oil and theviscosity of the water or brineflooding media results in poor recovery efficiency. When this differenceis great enough, an aqueous flooding medium will tend to finger throughthe high viscosity oil and thereby bypass most of the available oil. Theproblem of obtaining efficient oil recovery is further aggravated by thefact that there are virtually no oil-bearing formations of uniformpermeability. Rather, the typical oil-bearing formation consists ofmultiple layers of rock having different and often widely varyingpermeabilities relative to aqueous or oil liquid flow. There are manypockets or channels in the subterranean formation. These channels aremerely cracks or disuniformities in the rock structure. They can becharacterized as being paths of very low resistance to flow.

In such instances, it is apparent that a flooding medium will tend toselectively follow the course of least resistance, e.g., a zone of highpermeability, and thus quickly penetrate and bypass the oil. Under theseadverse conditions, the producing wells are soon producing so much ofthe flooding medium in relation to oil that the secondary recoveryprocess can no longer by operated economically. i

Most of these problems have been avoided by the addition ofviscosity-increasing agents to the flooding medium. Fatty acid soaps,aliginates, sucrose, glycerine, carboxymethylcellulose, andwater-soluble polymers such as polyvinyl alcohols, polyallyl alcoholsand hydrolyzed polyacrylamides have been suggested for use as agents inaqueous flooding medium. The addition of these agents increased theviscosity of the flooding medium. This increased viscosity floodingmedium, when injected into the subterranean formation at the input well,tends to plug the channels. The fact that the channels of highpermeability are blocked results in the flooding medium being forced topass through the oil containing formations, thus increasing the amountof oil extracted, and resulting in a more uniform hydrostatic face.However, these techniques have been found to be inadequate. Theintroduction of these viscosityincreasing agents is quite satisfactoryin blocking and plugging up channels in the initial sections of theformation nearest the input well. As the flooding medium is forcedfurther along in the formation it tends to become diluted by water whichis found throughout the formation. In addition, the viscosity increasingadditives tend to be lost in the reservoir rock surface. As a result ofthis dilution, the blocking or plugging ability of the flooding mediumis diminished until at some point in the formation the flooding mediumhas been so diluted that it no longer blocks the channels at all.

The present invention is based upon the discovery that a stable liquiddispersion of a water-soluble anionic vinyl addition polymer and awater-soluble cationic polymer can be injected into a producing wellwhich penetrates the formation, the result being that the channels inthe area surrounding the producing well, as well as the inner portionsof the subterranean formation are plugged with a polymeric substance.This phenomenon is due to the fact that the stable liquid dispersioncontaining the water-soluble anionic vinyl addition polymer and watersoluble cationic polymer is capable of being inverted in water wherebythe water-soluble vinyl addition polymer is released into water as asolution. This results in an uniformly viscous solution throughout theformation without the dilution and adsorption problems of the prior art.

The consequences of this procedure will cause increased produced oil towater ratios for a certain volume of water sent through the subterraneanformation.

' Thus, the total amount of water needed to be sent through theformation will be reduced.

OBJECTS It is an object of this invention to increase the oil to waterratio in the secondary recovery of oil from subterranean formations.

It is also an object of this invention to provide a stable liquiddispersion of a water-soluble anionic vinyl addition polymer and awater-soluble cationic polymer, which stable liquid dispersion iscapable of being in verted in water whereby the polymer is released intowater as a solution for recovering petroleum from a subterraneanoil-bearing formation.

Further objects will appear hereinafter.

THE INVENTION This invention relates to a process for reducing theamount of water removed from a producing well of a water floodingprocess for recovering petroleum from a subterranean oil-bearingformation which comprises introducing a stable liquid dispersion of awater-soluble anionic vinyl addition polymer and a water-solublecationic polymer into a producing well which penetrates the formation.The stable liquid dispersion is characterized as capable of beinginverted in water and the anionic vinyl addition polymer instantantlyreacts with the cationic polymer to produce a reaction product which maybe described as a three-dimensional water and hydrocarbon liquidinsoluble gel-like structure.

As mentioned above, the stable liquid dispersion is pumped into theproducing or output well. Once in the formation and upon contact withthe water in the formation, the stable liquid dispersion is inverted andthe polymers react as described above to form the gel-like structure.This structure is by nature oleophilic, and resists passage of aqueousfluids but promotes oil flow through the treated formation.

The stable liquid dispersion is generally prepared by diluting adispersion concentrate with an organic liquid. The dispersionconcentrate is a water-soluble anionic vinyl addition polymer in theform of a water-inoil emulsion which contains dispersed therein thefinely-divided water-soluble anionic vinyl addition polymer. Thisdispersion concentrate contains uniformly distributed therethroughout awater-soluble cationic polymer. The water-soluble anionic vinyl additionpolymers that are used in the practice of the invention may beillustrated by the following list of polymers:

TABLE I Number Name I Polyacrylic acid-sodium salt 7. Polymethacrylicacid-sodium salt 3 Maleic anhydride-vinyl acetate copolymer 4 Polyvinylmethyl ethermaleic anhydride copolymer Methacrylic acid-acrylamidecopolymer 6 Polyacrylic acid 7 lsopropenyl acetate-maleic anhydridesodium salt 8 ltaconic acid-vinyl acetate 9 Methyl styrene-maleicanhydride sodium salt Styrene-maleic anhydride Methylmethacrylatemaleicanhydride sodium salt Acrylic acid-styrene Acrylamide-aerylic acid (5%by weight) Acrylamide-acrylic acid (50% by weight) Polystyrene sulfonicacid Acrylamidmacrylic acid (80% by weight) The above polymers may varyin molecular weight. They may be as low as 10,000 or as high as12,000,000 or more. In many of the more useful applications, which willbe more fully discussed hereafter, the molecular weight will be greaterthan 1,000,000.

The invention contemplates using as preferred watersoluble anionic vinyladdition polymers the homoand copolymers of acrylic acid as well as thewater-soluble salts thereof.

THE WATER-SOLUBLE CATIONIC POLYMERS These polymers also may be selectedfrom a wide variety of known polymeric materials. Several of thesepolymers are listed below in TABLE II.

TABLE II Number Name 1 Ethylene dichloride-ammonia condensation polymers2 Tetraethylcne pentamine-epichlorohydrin condensation polymers 3Epichlorohydrin-ammonia condensation polymers 4 Polyethylene imine 5Ethylene diaminc 6 Polydiallyl amine 7 Dimethylamino ethyl methacrylate8 The methyl chloride quaternary of Number I 9 The benzol chloridequaternary of Number 7 l 0 Guanidine formaldehyde condensation polymersAcrylamide-diallylamine (30%) The above polymers are illustrative oftypical watersoluble cationic polymeric materials that may be used inthe practices of the invention. A preferred class of these polymers maybe described as alkylene polyamines which are illustrated by polymers 1,2, 3, 4, 5 and 8 above.

Many of the above polymers have been described with respect to thereactants from which they are prepared. A detailed discussion of theabove polymers and other cationic polymers appears in Canadian Pat. No.731,212, the disclosure of which is incorporated herein by reference.The polymers may be employed as solutions or in the form of awater-in-oil latex emulsion. When the polymers are of the vinyl additiontype they may be copolymers of other ethylenically saturated monomers.Such copolymers should contain at least 5 percent by weight of thecationic monomer.

THE ANIONIC VINYL ADDITION POLYMER POLYMERIC LATEX The inventioncontemplates utilizing the watersoluble anionic vinyl addition polymersin the form of water-in-oil emulsion which contains dispersed thereinthe water-soluble anionic vinyl addition polymer. Emulsions of this typeare prepared by dispersing the anionic vinyl addition polymer into awater-in-oil emulsion. These polymers as produced by most manufacturingprocesses are in the form of powders or lump-like agglomerates ofvarying particle size. It is desirable that the particles, before beingplaced into the emulsion, be comminuted by grinding, abrading or thelike so that their average particle size is less than 5 millimeters andpreferably is within the range of l to 5 microns. After the powders havebeen comminuted, they may be dispersed into the water-in-oil emulsion bymeans of agitation provided by such devices as stirrers, shakers and thelike. To be commercially practical, the amount of polymer in theemulsion should be at least 2 percent by weight. The inventioncontemplates using emulsions containing between 5 to percent by weightwith preferred emulsions having a polymer concentration within the rangeof 10 to 45 percent by weight. In some cases the starting emulsions areconverted to suspensions due to the nature and the amount of the polymerpresent therein.

From a commercial standpoint it is beneficial that the polymer emulsionsthus described be stable, yet at the same time contain relatively largeamounts of polymers. One method of insuring that the polymers do notprecipitate when dispersed in the emulsion is that the particle size ofthe polymer be as small as possible. Thus polymers dispersed in theemulsifiers are quite stable when the particle size is within the rangeof 5 millimicrons up to about 5 microns. To produce particle sizeswithin these limitations, spray dryers with appropriate size nozzles maybe used. It also is possible to prepare the polymer-containing emulsionof the watersoluble vinyl addition polymers directly from the vinylmonomers from which these polymers are synthesized. Suchpolymer-containing emulsions may be synthesized by using thewater-in-oil emulsion polymerization technique set forth in U. S. Pat.No. 3,284,393. The teachings of this patent comprises forming awater-inoil emulsion of water-soluble ethylenic unsaturated monomers.The emulsion is formed by utilizing a waterin-oil emulsifying agent. Tothis monomer is added a free radical-type polymerization catalyst andthe heat is applied under free radical-forming conditions to formwater-soluble polymer latices. The polymeric latices produced by thispatent are relatively unstable and frequently must be treated withadditional emulsifiers to render the products stable.

The water-in-oil emulsions used to prepare the above polymers may beformulated by any number of known techniques.

The oils used in preparing these emulsions may be selected from a largegroup of organic liquids which include liquid hydrocarbons andsubstituted liquid hydrocarbons.

A preferred group of organic liquids are the hydrocarbon liquids whichinclude both aromatic and aliphatic compounds. Thus, such organichydrocarbon liquids as benzene, xylene, toluene, mineral oils,kerosenes, naphthas and, in certain instances, petrolatums may be used.A particularly useful oil from the standpoint of its physical andchemical properties is the branch-chain isoparaffinic solvent sold byHumble Oil and Refining Company under the Tradename ISO- PAR M. Typicalspecifications of this narrow-cut isoparaffinic solvent are set forthbelow in TABLE III.

rAiaLi: in

Specification Properties Mini- Maxi mum mum Test Method Gravity, API at60/60F. 48.0 51.0 ASTM D 287 Color, Saybolt 30.0 ASTM D 156 AnilinePoint, "F. 185.0 ASTM D 611 Sulfer, ppm 10.0 ASTM D 1266 (Nephelometricmod.) Distillation, F. ASTM D 86 IBP 400.0 410.0 Dry Point 495.0 Flashpoint, F. (Pensky- Martens closed cup) 160.0 ASTM D 93 niques. In mostinstances, however, it is desirable that,

the emulsion be a stable emulsion and to achieve this end it is oftennecessary to employ an oil soluble emulsifying agent. The amount ofemulsifying agent to provide an emulsion will have to be determined byroutine experimentation. As a general rule it may be said that theamount of oil soluble emulsifier may range from 0.1 to 30 percent byweight based on the weight of the oil. To produce stable emulsions theamount of emulsifier will normally be within the range of 12 to 20percent by weight of the oil.

Rather than provide a listing of suitable emulsifiers, recommended asbeing satisfactory are the so-called PREPARATION OF THE DISPERSIONCONCENTRATE Once the latices containing the water-soluble anionic vinyladdition polymers are prepared, the dispersion concentrate is preparedby combining them with the water-soluble cationic polymers by theutilization of conventional mixing techniques. Preferably thewatersoluble cationic polymers are in the form of aqueous solutionswhich contain 5 to by weight of the polymer and are added to thepolymeric latex. Alternatively, they may be nearly water-free. Afteruniformly mixing the two components there results a dispersionconcentrate of a water-soluble anionic vinyl addition polymer and awater-soluble cationic polymer. The proportions of the two polymers maybe varied to a considerable degree. For instance, the ratio of thewater-soluble anionic vinyl addition polymer to watersoluble cationicpolymer may vary between 1:10 to 10:1 on a weight basis. A preferredratio is 1:5 to 5:1. The most preferred ratio is 1:2 to 2:1.

The amount of the water-soluble vinyl addition polymers plus thewater-soluble cationic polymers present in the finished dispersionconcentrate may be varied over a wide range of concentrations, e.g.dispersion concentrates containing from 0.001 to 75 percent by weightare useful, although for most applications the total weight of the twopolymers contained in the dispersion concentrate will be within therange of 5 to 40 percent by weight, with a very beneficial dispersionbeing one which contains between 10 to 30% by weight of the twopolymers.

The finished dispersion concentrates are stable at room temperature forperiods of time ranging between several days to as long as six monthssince they may be prepared over a wide variety of concentrations.Dispersion concentrates containing large amounts of polymers may beprepared and shipped to a use point and then diluted with an organicliquid just prior to use.

To illustrate the preparation of dispersion concentrates, a variety ofemulsions were prepared containing different water soluble anionic vinyladdition polymers. These emulsions are set forth below in TABLE IV.

TABLE IV Compo- W Water Oil Percent sition by by in emul' Polymerparticle number weight) weight) Polymer sion I size range 72 28(1) 93%acrylamide, 7% methacrylic acid 3 5 0.05-7.0 microns. 72 28(1) 93%acrylamide, 7% methacrylic acid... 35 0.05-7.0 microns. 72 28(T) 70%acrylamide. 30% acrylic acid 35 0.057.0 microns. 67 33(1) 93%acrylamide, 7% methacrylic acid.. 32 30 microns. 70 30(I) 70%acrylamide, 30% acrylic acid 34 .01-10 microns.

I 71 29(I) Sodium Polyacrylate 37 1 mm.

l= Isopar M.

T=Toluene.

low HLB materials which are well documented in the literature and aresummarized in the Atlas I-ILB Surfactant Selector. Although theseemulsifiers are useful in producing good water-in-oil emulsions, othersurfactants may be used as long as they are capable of producing theseemulsions. For instance, we have found that certain high I-ILBsurfactants are capable of producing stable water-in-oil emulsions. Atypical low I-ILB emulsifier is sorbitan monooleate.

DISPERSION CONCENTRATE A DISPERSION CONCENTRATE B To COMPOSITION NUMBERVI in TABLE IV, there was added an aqueous dispersion which contained 25percent by weight of an ammonia ethylene dichloride polymer of the typeused in DISPERSION A above, with the exception it had been quaternizedwith methyl chloride.

To illustrate other novel dispersion concentrates of the invention TABLEV is presented below:

TABLE V Dis- Anionic per- Latex by by sion Table IV Weight CationicPolymer Weight C l 60 20% solution of a tetra- 40 ethylene pentamineepichlorohydrin reaction product (Canadian Pat.

731,2!2) D VI 50 Ethylene diamine 10 E V 70 75% acrylamide,

methylamino ethyl methacrylate copolymer in the form of a latex(water-inoil) See TABLE II,

U. S. 3,624,0l9

All of the above dispersion concentrates were stable and were capable ofbeing stored under a variety of conditions without inter-reaction of thetwo polymers.

THE ORGANIC LIQUID Generally, the dispersion concentrate will be dilutedwith an organic liquid just prior to use. As mentioned above, thepreferred dispersion concentrate will have from to 40 percent by weightof the two polymers. In this application, the dispersion concentratewill be diluted with the organic liquid so that the stable liquiddispersion will have 0.00] to 10 percent by weight of the two polymers.

The dispersion concentrate can be diluted with the organic liquid(including crude oil) near the location of the well where it is to beused. This on-site dilution procedure may be performed in a mixing tanknear the well location and then be pumped directly into the well. Theorganic liquids of this invention include both aromatic and aliphatichydrocarbon compounds. Thus, such organic hydrocarbon liquids asbenzene, xylene, toluene, mineral oils, kerosene, naphthas andpetroleums may be used. In particular, the petroleum recovered from theprimary recovery operation (crude oil) may be used to dilute thedispersion concentrate for use. The use of petroleum obtained from theprimary recovery operation eliminates the burdensome problems inhandling other organic liquids but also results in a great decrease incost.

Oftentimes it is desirable to use a more concentrated flooding mediumthan the ones as defined above. If such is the case, the dispersionconcentrate may be used without dilution with an organic liquid. If suchis the case the polymeric latex concentrate would be pumped directlyinto the well without any type of dilutron.

INVERSIONS OF THE STABLE LIQUID DISPERSION One of the most interestingphenomenon that occurs in working with the above described anioniclatices is the fact that under certain conditions the emulsion, whichcontains dispersed therein the finely-divided water-soluble anionicvinyl addition polymers, may be inverted.

The water-soluble anionic vinyl addition polymercontaining emulsions maybe inverted by any number of means. The most convenient resides in theuse of a surfactant added to either the polymer-containing emulsion orto the water into which it is to be dissolved. The placement ofasurfactant into the water causes the emulsion to rapidly invert andrelease the polymer in the form of an aqueous solution. When thistechnique is used to invert the polymer-containing emulsion the amountof surfactant present in the water may vary over a range of 0.01 to 50percent based on polymer. Good inversion often occurs within the rangeof 1.0 to 10 percent based on polymer.

The preferred surfactants are hydrophilic and are further characterizedas being water soluble. Any hy drophilic-type surfactant such asethoxylated nonyl phenols, ethoxylated nonyl phenol formaldehyde resin,dioctyl esters of sodium sulfosuccinate, and octyl phenol polyethoxyethanol can be used.

Other surfactants that may be employed include the soaps such as sodiumand potassium myristate, laurate, palmitate, oleate, stearate, resinate,and hydroabietate, the alkali metal alkyl or alkylene sulfates, such assodium lauryl sulfate, potassium stearyl sulfate, the alkali metal alkylor alkylene sulfonates, such as sodium lauryl sulfonate, potassiumstearyl sulfonate, and sodium cetyl sulfonate, sulfonated mineral oil,as well as the ammonium salts thereof; and salts of higher means likelauryl amine hydrochloride, and stearyl amine hydrobromide.

Any anionic, cationic or nonionic compound can be used as thesurfactant.

In addition to using the water soluble surfactants described above,other surfactants may be used such as silicones, clays and the likewhich are included as surfactants since, in certain instances, they tendto invert the emulsion even though they are not water-soluble.

In other specific cases the surfactant may be directly added to thepolymer-containing emulsion; thereby rendering it self-inverting uponcontact with water. These products, while capable of being used incertain systems, must be carefully formulated since the surfactants maytend to interact with the emulsifier or the emulsion and destroy itprior to its being used.

The emulsions may be inverted by treating them with aqueous solutions ofalkaline materials such as solutions of sodium hydroxide, ammonia,amines, sodium aluminate or the like.

Other techniques for inverting the emulsions include the use ofagitation, high voltage electrical fields, heat and pH shift, as well asthe placement into the water, into which the polymer-containing emulsionis to be dissolved, certain electrolytes. For any particularpolymer-containing emulsion a suitable method for its inversion may bereadily determined by routine experimentation.

THE GEL-LIKE STRUCTURES When the stable liquid dispersions are thusinverted the anionic vinyl addition polymer instantly reacts with thecationic polymer to produce within a matter of minutes a reactionproduct which may be described as a three-dimensional, water andhydrocarbon liquid insoluble gel-like structure, which is composed ofwhat is believed to be ionically combined intimate admixture EXAMPLESWhen the water-in-oil emulsions are injected into producing walls theyhave a high water to oil output ratio, generally resulting from manyyears of secondary recovery operations, it is possible to greatlyimprove the amount of oil produced in relation to the water recovered.

For instance, when the water-in-oil emulsions would be used to treattypical produced fluid from, for instance, a West Texas water floodingfield improvements in the amount of oil produced will range from between20 to as high as 40 percent by weight.

Specifically, when the water-in-oil emulsions of the invention are usedtypical results that would be obtained are set forth in Table VI below.Typical of the dilutions used are injection fluid which is composed of95 percent crude oil, 4 percent water, 1 percent polymer. The resultsshown in Table VI would be obtained on dispersion concentrates A throughE, as described above, after continuous injection would be made into tsiia in .9t2,.1,19.5. skiwri While the invention has been'described withrespect to producing wells of water flooding processes, such is intendedto include primary production wells which produce crude oil and water.The invention is of particular importance where the produced fluid has ahigh water ratio. It is not unusual to find primary wells producing 100barrels of brine for each 5 to barrels of crude oil. Depending upon thegeological and chemical nature of the producing rock formation,- alongwith the proper choice of polymers, exhibited; will be exhibited; i.e.,reduction in produced water.

I claim:

1. A process for reducing the amount of water removed from a producingwell used for recovering petroleum from a subterranean oil-bearingformation which comprises the steps of introducing a stable liquiddispersion of a water-soluble anionic vinyl addition polymer and awater-soluble cationic polymer into a producing well which penetratessaid formation, said dispersion comprising a polymeric latex composedofa water-in-oil emulsion which contains dispersed therein afinely-divided water-soluble anionic vinyl addition polymer, saidpolymeric latex having uniformly distributed therethroughout awater-soluble cationic polymer with the weight ratio of polymeric latexto watersoluble cationic polymer being within the range of 1:10 to 10:1and the total amount of polymeric latex plus water-soluble cationicpolymer present within said dispersion being within the range of from0.001 to per cent by weight and then inverting said dispersion withinthe subterranean formation whereby a three dimensional, water andhydrocarbon liquid insoluble gel-like structure is produced.

2. The process of claim 1 wherein the stable liquid dispersion iscomprised of a polymeric latex composed of a water-in-oil emulsion whichcontains dispersed therein a finely-divided polyacrylic acid or awatersoluble salt thereof, said polymeric latex having uniformlydistributed therethroughout a water soluble alkylene polyamine polymerwith the weight ratio of polymeric latex to water-soluble cationicpolymer being within the range of 1:10 to 10:1 and the total amount ofpolymeric latex plus water-soluble cationic polymer present within saiddispersion being within the range of from 0.001 to 75 percent by weightand the dispersion is inverted by means of a surfactant.

3. The process of claim 1 wherein the stable liquid dispersion has aweight ratio of polymeric latex to water-soluble cationic polymer withinthe range of from 1:5 to 5:1 and the amount of polymeric latex pluswater-soluble cationic polymer present within said dis persion is withinthe range of from 5 to 40 percent by weight and the dispersion isinverted by means of a surfactant.

41. The process of claim 1 wherein the stable liquid dispersion has aweight ratio of polymeric latex to water-soluble cationic polymer withinthe range of from 1:2 to 2:1 and the amount of polymeric latex pluswater-soluble cationic polymer present within said dispersion is withinthe range of from 10 to 30 percent by weight and the dispersion isinverted by means of a surfactant.

5. The process of claim 1 where the water-soluble anionic polymer ispolyacrylic acid or its water-soluble salts and the water-solublecationic polymer is an alkylene polyamine polymer and the dispersion isinverted by means of a surfactant.

2. The process of claim 1 wherein the stable liquid dispersion iscomprised of a polymeric latex composed of a water-in-oil emulsion whichcontains dispersed therein a finely-divided polyacrylic acid or awater-soluble salt thereof, said polymeric latex having uniformlydistributed therethroughout a water soluble alkylene polyamine polymerwith the weight ratio of polymeric latex to water-soluble cationicpolymer being within the range of 1:10 to 10:1 and the total amount ofpolymeric latex plus water-soluble cationic polymer present within saiddispersion being within the range of from 0.001 to 75 percent by weightand the dispersion is inverted by means of a surfactant.
 3. The processof claim 1 wherein the stable liquid dispersion has a weight ratio ofpolymeric latex to water-soluble cationic polymer within the range offrom 1:5 to 5:1 and the amount of polymeric latex plus water-solublecationic polymer present within said dispersion is within the range offrom 5 to 40 percent by weight and the dispersion is inverted by meansof a surfactant.
 4. The process of claim 1 wherein the stable liquiddispersion has a weight ratio of polymeric latex to water-solublecationic polymer within the range of from 1:2 to 2:1 and the amount ofpolymeric latex plus water-soluble cationic polymer present within saiddispersion is within the range of from 10 to 30 percent by weight andthe dispersion is inverted by means of a surfactant.
 5. The process ofclaim 1 where the water-soluble anionic polymer is polyacrylic acid orits water-soluble salts and the water-soluble cationic polymer is analkylene polyamine polymer and the dispersion is inverted by means of asurfactant.